Syntheses of Transition Metal Complexes Containing a Naphthyridine Dicarboxylate Ligand and Catalytic Activity Study
Date Issued
2014
Date
2014
Author(s)
Lee, Chia-Han
Abstract
Dimetallic complexes are known to have unique properties in transition metal catalyzed reactions, and there are a lot of examples proving the cooperation between metals during the catalysis. Therefore, there is a need to design and synthesis of multi-dentate ligands for construction of dimetallic systems.
In this research, 1,8-naphthyridine-2,7-dicarboxylate was used as the multi-dentate ligand for complexation with ruthenium, copper and cobalt ions to form Cu2(I, I), [Co2(II, II)]2 and Ca[Ru2(II, II)]2. Moreover, we successfully disclosed their absolute structures by crystals.
Naphthyridine dicarboxylate ligand can capture two metal ions to form two five-member rings with N and O donors. Such a dicarboxylate ligand not only has strong coordinating ability but also stabilizes metal centers with high oxidation state. Because of the H-bonding interaction between carboxylate groups and protic molecules, the ligand readily assists the solubility of the resulting complexes in protic solvents like water, methanol and ethanol.
Industrial application on oxidative cleavage of olefins usually go through ozonolysis. However, chemists are still looking for environmental-friendly alternatives with higher efficiency. In the past, ruthenium-catalyzed oxidative cleavage reaction usually works in water-organic co-solvent system. Surprisingly, Ca[Ru2(II, II)]2 can catalyzed this reaction in water with great performance. Kinetic
experiment also suggests that binuclear structure really assists the cleavage reaction.
Subjects
萘啶
雙金屬
羧酸根
Type
thesis
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